Chlorhydrins and process of making same.



-HENRY v. WALKEB, or

UNITED STATES PATENT OFFICE.

nnooxmm, Nnw ronx, assrcnon To run mans & WALD- STEIN COMPANY, OF NEWARK, NEW JERSEY, A CORPORATION OF NEW JERSEY.

CHLOBHYDRINS AND PROCESS OF MAKING SAM-E.

No Drawing.

Specification of Letters Patent. Application filed January 21, 1908. Serial No. 478,497.

Patented Oct. 18, 1910.

the same, and its novelty consists in the several successive steps of the processemployed.

In a co-pending application for Letters Patent of the United States, filed January 21, 1909, and bearing Serial No. 473,499, I have described a process for the preparation of a novel solvent for pyroxylin and other substances. This solvent consists mainly of olefin oxids produced by subjecting chlorhydrins to the action of caustic alkahes, for instance, caustic lime. The production of a suitable body of chlorhydrins is an incident in that process, but the material from which it is produced constitutes a source of supply heretofore unsuspected, and the process of its manufacture mvolves steps and reactions heretofore undiscovered, and it is, therefore, made the subject matter of this separate application for Letters Patent.

The source-of supply of the material to be treated is any material containing a suitable body of unsaturated hydrocarbons, for

instance, the oil. produced from Scotch shale oil, or by the destructive distillation of various kinds of brown coal. But the material which I prefer to employ is so-called gas naphtha. This is a by product of the ordinary commercial treatment of petroleum. Thus, in the process of refining crude petroleum, the oil is subjected to distillation, the lighter products, such as naphtha and benzin, coming over first. These are followed by the, burning oil fraction. At a certain stage of this period of the distillation, it is found that the product coming over is of much lower boiling point, ravity and flashing point than that prece ing it. This peculiarity is attributed to a cracking up of the higher hydrocarbons under the influence of the high temperature prevailing in the distillation. It is usual to run the distillation until the product has again risen in gravity, etc, to that of the initial burning oil fraction. This-secondary product which is collected separately is then redistilled,

. prises yielding a distillate called gas-naphtha and a residue which is added to the burning oil fraction. This material known in the refineries as gas-na htha has been so called from the use to which it has heretofore been put, namely, the manufacture of gas for heating purposes and the enrichment of illuminating gas.

Whereas American petroleum consists almost exclusively of saturated hydrocarbons or paraflins the gas-naphtha contains about 40% of olefins and about only of paraffins. Its boiling point ranges from 35 to 125 centigrade. It is believed that its olefins range from 5 to 8 carbons and that they are primary in structure. For example, the C olefin may be represented by the formula CH,-CH CH,CH CH=CH,.

It might be thought that such a mixture of olefins and parafiins as is contained invthis gas-naphtha would react with hypochlorous acid produced in any of the usual ways to form chlorhydrins (although so far as known to me no chlorhydrin or oxid of a primary olefin having five or more carbons has been so roduced) but it was found not to be so. T ere are two described methods of preparing hypochlorous acid. The first of these depends essentially upon the reaction of chlorin with mercuric oxid. This method is too expensive to be thought of on account of the great cost of the mercuric oxid em loyed. The second of these comt e treatment of hy ochlorites of sodium, or calcium, with a dilute acid. In each case free chlorin was present, the yield of hypochlorous acid was small and its solution was dilute. Both of these methods, therefore, were, unavailable. l was, therefore, obliged to find another method of producing the hypochlorous acid.

I discovered that if there was added to a solution of a suitable hypochlorite, for instance, hypochlorite of soda, :1 sufiicient quantity of a suitable bicarbonate, for instance, bicarbonate of soda, to convert both the free alkali and the-sodium in combination in the hypochlorite, into sodium carbonate, then a solution was obtained which contained hy ochlorous acid, free from chlorin and w iich reacted readily with the olefins of the gas-naphtha; This process of producing hypochlorous acid free from Q and it is made the sub'ect matter of a sepawith to form 'hypochlorousacid; A proper rate. application for Unite States, filed January 21, 1909, and

bearing Serial No. 473,498. I In the practice of my process of making ehlorhydrms, the gas-naptha, comprising a mixture of olefins and paraflins as state or other suitable material containing the olefins, is first placed in a vessel provided with means for agitatin and coolin .its contents. In another suitaile vessel is aced a solution in water of asuitable hypoch orite, for instance, hypochlorite of soda, dissolved in water. It is referable to use a separate vessel as stated, at not at all essential, since the gas-naphtha, hypochlorite and bicarbonate of soda or the equivalent materials may be all three mixed together and allowed to react in the same vessel. A solution of the hypochlorite containing from 15 ;to 25 per cent. of NaOCl is of convenient strength. To this is added. a s'ufiicient quantity of a soluble bicarbonate of a fixed alkali, referably bicarbonate. of soda, to react t ereproportion to employ is about.75 parts of the hypochlorite of soda (NaOCl) to about 85 arts of the bicarbonate of soda (Na 00,). The bicarbonate may beadded in the form of a saturated a ueous solution, or mixed with an amount 0 water insufliv cient for solution or in the dry state. There is no free chlorin produced. he mixture of hypochlorite and bicarbonate of soda in whlch the hypochlorous acid is formed is then added to the vessel containing the gas naphtha, or other material, and the contents are agitated and'cooled. The reaction will take place at ordinary temperatures without cooling, but the best results are obtained by preventing the-rise, of temperature due to the reaction and maintaining the temperature ator below 15 centigrade. This reaction should continue for about four hours. At the end of that time the oily portion of the liquid containing the chlorhyd'rins is allowed to separate from the aqueous portion of the liqui the latter being drawn ofi' and rejected. The oily portion is then washed with a small amount of water toremove an h gochlorite which might remain and it 1s eydrated. If it is desired to accom lish may be employed. If time is not essential,

chlorhydrins remain in t e oily part of the liquid and not in its a ueous part. The parafiins, or residual h rocarbons, which are mixed with the ch orhydrins arethen removed. This is accomplished by distillation at a'suitable tem erature below the boiling'point of the chlor ydrins, which 18 about tters Patent of the hydrins will be carried over.

the decomposition o Uhem 170 centlgrade. Such a temperature is.

about 140 eentigrade. Of course, the temperature during this step of the process must be lower than that at which the chlor- After such distillation, the residual liquid consists of the chlorhydrins sought to be obtained.

The reactions apparently involved may 0 be illustrated in connection with the olefin I a 1) NaOOH- NaHCO, Na,C0, HOCl.

(2) (LI-I HOCl C,H,, OHOl (Chloriydrln ot the G. olefin) In carrying out the above process, it is advisable first to ascertain the percentage of olefins in the material employed by determining the amount of bromin absorbed,

using the well known methods for this purpose. From this, the quantity of .hypochlorous acid necessary. to be used is shown by the above equation No. 2, a slight excess of such acid being used to insure as complete a conversion of the olefins as possible.

The mixture of chlorhydrins above described is a yellowish liquid having a char acteristic camphe'r-like odor, insoluble in water, miscible with such organic solvents as alcohol, ether'or benzin,-having a specific gravity'ranging from about 1.015 to about 1.045 at .15 C., tending to darken when distilled, (a iparently on account of istic chemical prope of being decomposed by'caustic alkali the removal of hydrochloric acid, and the formation of olefin the higher chlorhydrins in the mixture) and having the characteroxids. These olefin oxids, and consequently the chlorhydrinsfrom which they are derived by' decomposition with caustic alkali as just stated, are of prima structure. This is demonstrated by thefo owing considerations: f th h d t 1. The ori o e -nap t a pro uc from which di chlorlfirins are derived shows that the atter are of prime structure because it is well known that t eparafiins of petroleum are of primary structure and it has been shown by actual chemical investi tion (see Armstrong and Miller 00. Transactions 1886, I, 79-93,-Be1-. (Rei) XIX, 244) that the action of heat upon said paraflins produces fins. It follows, therefore, t at the gasnaphtha olefins used as an initial material of the products of my present invention are likewise of primary structure, and therefore the chlorhydrins derived therefrom must also beprimary.

2. It is a known characteristic property of rima olefin oxids (see Eltekow Ber. X 396) that they do not combine with water, whereas the secondary and tertiary oxids do combine with water to form glyrimary ole-- erases cols. Since the olefin oxids derived from the clalorhydrins of my present invention do not combine with water, it follows that they must be of primary structure.

I claixni 1. The process of making chlorhydrins which consists in mixin a bicarbonate of a fixed alkali and a solution containing a hypochlorite of a fixed alkali and reacting therewith upon an olefin.

2. The process of making chlorhydrins which consists in first mixing a bicarbonate of a fixed alkali and a solution containing a hypochlorite ofa fiired alkali, second agitat ng an olefin therewith, and at the same time preventing any rise of temperature due to the reaction.

3. The process of making chlorhydrins which consists first in subjecting a solution of a hypochlorite containing anexoess of free alkali to the action of a bicarbonate of a fixed alkali in excess, whereby there results an alkaline solution of hypochlorous acid free from chlorin, and reacting therewith upon an olefin.

a. T e process of making olefin chlorhydrins having five carbons and over, consisting in mixing a bicarbonate of a fixed alkali and a solution containin a hypochlorite of a fixed alkali, reactin i nerewith upongas naphtha, separating t e oily layer contaming the chlorhydrins from the aqueous, layer, and fractionating the oily layer to obtain the chlorhydrins therefrom..-

5. ihe process of making olefin chlorhydrins having five carbons and over consist,- in in first mixing a bicarbonate of a fixed alali and a solution containing a hypochlorite of a fixed alkali, second, agitating gas naphtha therewith, and at the same time preventing any rise of temperature due to the reaction, and third, se arating the oily layer containing the chlor gdrins from the aqueous layer, and fourth, actionating the liquid so separated to obtain the chlorhydrins therefrom;

6. As new products of manufacture, the

chlorhydrins of the primary olefins having five or more carbons, being yellowish liquids having characteristic camphor-like odor, 111- soluble in water, miscible with such organic solvents as alcohol, ether or benzin, and having the characteristic chemical property ofbein decomposed by caustic alkali wit remova of h drochloric acid and formation of olefin oxi s which do not combine with water.

7. As a new product of manufacture, a

mixture of primary olefin chlorhydrins, be-

ing a yellowish liquid having characteristic camphor-like odor, being insoluble in water, miscible with such organic solvents as alcohol, ether or benzin, having specific gravity ranging f rox'n' about 1.015 to a specific gravity of about 1.045 at 15 6., tending to darken on distillation and having the characteristic chemical roperty oi being'decomposed by caustic al all with removal of h drochloric acid and the formation of ole n oxids which do not combine with water.

Witnessmyfihand this 19th day of January 1909, at ew York, N. Y.

- HENRY V. WKER. Witnesses;

-W1LLIAM R. Baum,

vALA C. MoDoNNnnn. 

